A process for preparing substituted polycyclo-alkylidene polycyclo-alkanes and the corresponding epidioxy compounds; as well as said substituted polycyclo-alkylidene polycyclo-alkanes and the corresponding epidioxy compounds.
The invention relates to a process for preparing substituted polycyclo-alkylidene polycyclo-alkanes and the corresponding epidioxy compounds, as well as to these substituted polycycloalkylidene polycyclo-alkanes and the corresponding epidioxy compounds.
The term "substituted polycyclo-alkylidene polycyclo-alkanes" as used herein comprises especially compounds of formula 44 of the formula sheet, in which A and B represent alkylene radicals, which alkylene radicals may be attached to each other via an alkylene radical C, and wherein R.sub.1 represents a substituent which, in the case of 4-equatorially R.sub.1 -substituted 2.2'-adamantylidene adamantanes, cannot be chloro, hydroxy, oxo, D or a radical of formula 1 of the formula sheet. In preferred compounds of formula 44, alkylene radical A contains 2 to 5 carbo atoms, alkylene radical B 2 to 5 carbon atoms, and alkylene radical C, if present, 1 to 4 carbon atoms. Examples of compounds of formula 44 are 4-eq-R.sub.1 -2,2'-adamantylidene adamantanes, 4-eq-R.sub.1 -9,9'-bicyclo [3,3,1]-nonylidene-bicyclo[3,3,1]-nonanes, 2- or 7-R.sub.1 -8,8'-bicyclo[3,2,1]-octylidene-bicyclo[3,2,1]-octanes and 2- or 7-R.sub.1 - 10,10'-bicyclo[4,3,1]-decylidene-bicyclo[4,3,1]-decanes, in which the two rings of each of the bicyclic radicals may be attached to each other via an alkylene bridge.
The corresponding epidioxy compounds--which contain a dioxetane ring--are especially compounds of formula 45, in which A, B and C, if present, have the above-mentioned meanings, and R.sub.2 represents a substituent which, in the case of 4-eq-R.sub.2 -2,2'-epidioxy-2,2'-adamantyl adamantane cannot be chloro or hydroxy.
The invention relates to these compounds and to processes for the preparation thereof. Especially, the invention relates to a process for preparing substituted polycyclo-alkylidene polycyclo-alkanes, in which a corresponding non-substituted compound is subjected to a halogenation reaction, using a halogenating agent in a solvent, and the halogenation product is recovered from the reaction mixture and/or, if desired, is subjected to a substitution reaction.
In Tetrahedron Letters 1970, 4579-82, J. H. Wieringa, J. Strating and H. Wynberg describe a process in which adamantylidene adamantane is reacted with chlorine is tetrachloromethane at a temperature of -20.degree. to +10.degree. C. to form 4-eq.-chloroadamantylidene adamantane in addition to polychlorinated products. The chloro-substituted adamantane compound is the starting point for further reaction in the presence of AgNO.sub.3 and THF/H.sub.2 O to form a mixture of the corresponding 4-hydroxy-adamantylidene adamantane compounds, which with the appropriate oxidant (Jones reagent: CrO.sub.3, H.sub.2 SO.sub.4, acetone) are finally converted into the corresponding ketone compound, in which the carbonyl group is in the 4-position.